镍催化芳香卤化物与溴代烯烃还原偶联成烯反应的研究

发布时间：2018-06-08 01:39

  本文选题：镍催化 + 偶联反应　； 参考：《上海应用技术大学》2017年硕士论文

【摘要】：本文发展了一种镍催化卤代芳烃与卤代烯烃的还原偶联反应,在较温和的条件下即可实现烯烃类化合物的高产率制备,该方法具有底物适应性好,化学选择性优异等特点。通过对卤代芳香化合物与烯基溴类底物的反应进行考察,发现该方法表现出了较好的空间选择性,从溴代烯烃的顺反混合物出发,主要得到反式烯烃的优势构象化合物;同时,该方法也表现出了良好的官能团耐受性,对于富(缺)电子卤代芳烃以及杂环溴代化合物,均能与(非)共轭烯基溴交叉偶联实现烯烃类化合物的制备。对于反应机理也进行了探讨,通过深入开展自由基捕获、锰粉代替锌粉作为还原剂等实验以及DFT(密度泛函理论)计算,提出了较为合理的反应机理推断。Ar-NiⅡ(L)-Ⅰ中间体的成功合成以及参与的实验,进一步验证了可能的反应机理。
[Abstract]:In this paper, a nickel catalyzed reduction coupling reaction of halogenated aromatics with halogenated olefins has been developed. The high yield of alkenes can be prepared under mild conditions. The method has the advantages of good substrate adaptability and excellent chemical selectivity. The reaction of halogenated aromatic compounds with alkenyl bromine substrates was investigated. It was found that the method showed good spatial selectivity. The dominant conformational compounds of trans-olefin were obtained from cis / trans mixtures of brominated olefin. This method also shows good functional group tolerance. For electron-rich halogenated aromatics and heterocyclic brominated compounds, they can be cross-coupled with (non-conjugated) enyl bromide to achieve the preparation of olefin compounds. The reaction mechanism was also discussed. Experiments such as free radical trapping, manganese powder replacing zinc powder as reducing agent and DFT (density functional theory) calculation were carried out. A reasonable reaction mechanism was proposed. The successful synthesis of the intermediate of Ar-Ni 鈪，

本文编号：1993799